The distribution of clay minerals from the N and S Atlantic Cretaceous deep-sea sediments is related to rifting, sea-floor spreading, sea-level variations and paleoceanography. Four main clay mineral suites were identified: two are inherited and indicative of ocean geodynamics, whereas the others result from transformation and authigenesis and are diagnostic of Cretaceous oceanic depositional environments. Illite and chlorite, together with interstratified illite-smectite and smectite occur above the sea-floor basalts and illustrate the contribution of volcanoclastic materials of basaltic origin to the sediments. Kaolinite, with variable amounts of illite, chlorite, smectite and interstratified minerals, indicates detrital inputs from continents near the platform margins. Kaolinite decreases upward in the series due to open marine environments and basin deepening. It may increase in volume during specific time intervals corresponding to periods of falling sea-level during which overall facies regression and erosion of the surrounding platforms occurred. Smectite is the most abundant clay mineral in the Cretaceous deep-sea sediments. Smectite-rich deposits correlate with periods of relatively low sedimentation rates. As paleoweathering profiles and basal deposits at the bottom of Cretaceous transgressive formations are mostly kaolinitic, smectite cannot have been inherited from the continents. Smectite is therefore believed to have formed in the ocean by transformation and recrystallization of detrital materials during early diagenesis. Because of the slow rate of silicate reactions, transformation of clay minerals requires a long residence time of the particles at the water/sediment interface; this explains the relationships between the observed increases in smectite with long-term sea-level rises that tend to starve the basinal settings of sedimentation. Palygorskite, along with dolomite, is relatively common in the N and S Atlantic Cretaceous sediments. It is not detrital because correlative shelf deposits are devoid of palygorskite. Palygorskite is diagnostic of Mg-rich environments and is indicative of the warm and hypersaline bottom waters of the Cretaceous Atlantic ocean.

The amorphous aluminosilicate allophane was synthesized by rapid mixing of inorganic solutions with high initial concentrations (10 – 100 mmol/l) followed by hydrothermal treatment. X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed homogeneous products having a hollow spherical amorphous structure with a particle diameter of 3 – 5 nm. The amorphous products had a high BET specific surface area (490 – 552 m2/g) in comparison with natural allophane and had a narrow pore-size distribution (2 – 5 nm in diameter). The results of water vapour adsorption isotherm studies showed a gradual increase over the range of relative water vapour pressure of 0.6 – 0.9 and reached a maximum of ∼85 wt.%. The synthetic allophane shows promise as an adsorbent material because of its high adsorption-desorption capacity and its unique structure.

Vermiculitization of mica is one of the main weathering processes in soils from three upland catchments receiving various levels of acid deposition. Usually this process is manifested by the presence of interstratified mica-vermiculite with the interlayer space in the vermiculite often partially filled with polymeric hydroxyaluminium species. In one peaty podzol, regularly interstratified mica-vermiculite clearly develops at the expense of mica and is the dominant mineral in the Eh horizon. It was concentrated by chemical treatments to remove organic matter, free iron oxides, and any Al species in the interlayer, and the structural formula calculated from chemical analysis confirmed the dioctahedral character of both vermiculite and mica components, and indicated that the vermiculitic weathering product was formed from a dioctahedral mica. The degree of interlayering in the interstratified phases seemed to be pH-dependent with resultant implications for soil and freshwater acidification.

Although natural Na-bentonite has little catalytic activity, various cation-exchanged bentonites have proved to be effective catalysts for a wide variety of organic reactions. In the presence of these catalysts alkenes can be induced to add (a) water, to yield branched-chain symmetrical ethers; (b) alcohols, to give a variety of ethers; (c) thiols, to yield thio-ethers; (d) carboxylic acids, to give esters. The number of products obtained in each reaction depends on the ease of rearrangement of the carbocation intermediates. High yields are obtained where a single carbocation intermediate is formed, A variety of elimination reactions is also catalysed by these sheet silicates. Water is eliminated from alcohols to produce ethers, ammonia is eliminated from amines to make secondary amines, and hydrogen sulphide is eliminated from thiols to give dialkyl sulphides. In most cases the ion-exchanged bentonites react as acidic heterogeneous catalysts.

The alteration and transformation behaviour of montmorillonite (bentonite from Wyoming, MX-80) in low-salinity solutions (NaCl, CaCl2) in the presence of metallic Fe (powder and 86461 mm plate) and magnetite powder was studied in batch experiments at 300ºC to simulate the mineralogical and chemical reactions of clays in contact with steel in a nuclear waste repository. The evolutions of pH and solution concentrations were measured over a period of 9 months. The mineralogical and chemical evolution of the clays was studied by XRD, SEM, Transmission Mössbauer Spectroscopy and TEM (EDS, HR imaging and EELS). Dissolution of the di-octahedral smectite of the starting bentonite was observed, in favour of newly formed clays (chlorite and saponite), quartz, feldspars and zeolite. The formation of Fe-chlorite was triggered by contact with the metallic Fe plate and Fe-Mg-chlorite at distance from the Fe plate (>2 mm).

The chemistry of smectites from some bentonite deposits derived from intermediate rocks has been examined by electron microprobe methods. A large variation in chemical composition within very short distances, principally controlled by a well-defined negative relationship between Si and A1, and between A1VI and Fe 3+ and A1VI and Mg has been observed. On the other hand, Mg does not vary systematically with either Si or Fe3+. In several bentonites beidellite coexists with montmorillonite and there is a compositional transition between the two smectite minerals, implying the existence of a possible solid-solution series. This transition occurs only when Cheto-type montmorillonites are present, being absent for Wyoming-type montmorillonites. No compositional transition between Wyoming-and Cheto-type montmorillonite was observed. It is believed that the compositional variations reflect initial chemical gradients originated during the devitrification of the volcanic glass, due to the migration of chemical components.

The results of detailed analyses of the samples discussed in part I are reported. The chemical, morphological and microstructural changes which occurred during moist curing and soaking have been determined using thermal analysis, X-ray powder diffraction analysis, and scanning and transmission electron microscopy combined with EDAX. The analytical results together with the physical observations have shown that the period of volume instability and swelling coincides with the period of gypsum consumption and ettringite formation. However, swelling is not caused by growth of crystalline ettringite but is the result of water absorption. An osmotic mechanism is proposed in which concentration gradients are generated within a surface colloidal layer on the clay particles. Ettringite rods nucleate and grow within this layer and C-A-S-H gel is produced in the areas between the rods. This results in concentration gradients at the clay particle surfaces which provide the driving force for osmosis. The implications of these findings are discussed in relation to lime- stabilization of soils.

The relationship between three parameters, the Tmax given by Rock-Eval pyrolysis, the illite content in illite-smectite mixed layers (I-S) and the Ku¨bler Index (KI) has been investigated in the Cretaceous–Neogene, sedimentary syn-orogenic successions in the Northern Apennines (Italy). A strong relationship was found between maturity stages of kerogen, illite content in I-S and KI. The oil formation zone for continental organic matter (Type III), delimited by Tmax between 434 and 465ºC, corresponded to rocks with short-range ordering R1, I-S with illite content between 60 and 85% and KI values in the range 0.85–0.65 (ºΔ2θ). Over-mature rocks were characterized by Tmax >465ºC, a long-range ordered I-S with an illite content >85% and KI in the range 0.65–0.45 (ºΔ2θ). The relationship permits use of both mineralogical parameters and Tmax to estimate palaeotemperatures in sedimentary successions and it can be exploited in hydrocarbon research to evaluate the petroleum potential.

The adsorption isotherm of methylene blue (MB) on sepiolite gels is of the Langmuir type, indicating a great affinity of the MB towards the sepiolite; the adsorption is quantitative up to adsorption of MB of 0·1 mmol/g sepiolite. The differences observed in the absorption spectrum in the region 500–650 nm for different MB loadings are interpreted in terms of aggregation of MB molecules on the sepiolite surface with the formation of MB dimers, trimers and higher aggregates. The progressive coverage of the sepiolite surface by MB produces a sharp decrease in the viscosity of the gels, and the suspension becomes peptized for an MB loading of 0·21 mmol/g which corresponds to the adsorption of MB dimers. These results indicate that MB avoids particle-to-particle interactions. The viscosity decrease is parallel to the perturbation of the Si-OH groups on the sepiolite surface as observed by IR spectroscopy, suggesting that these silanol groups can also play an important role in the rheological behaviour of aqueous sepiolite dispersions.

The acidity of Ni2+- and Co2+-exchanged montmorillonite has been probed using the diagnostic bases n-butylamine, cyclohexylamine and pyridine. Derivative thermograms for the desorption of pyridine from Ni2+- and Co2+-exchanged montmorillonite exhibited strong maxima at 40°, 90° and 360°C together with a weak maximum near 170°C The desorption maximum at 360°C is usually attributed to desorption of base from Bronsted acid sites. However, IR spectra of pyridine adsorbed on Ni2+- and Co2+-exchanged montmorillonite, at 250°C were dominated by intense bands near 1450 and 1607 cm−1 which are diagnostic of Lewis-bound pyridine. Consequently, the desorption maximum at 360°C must, in this instance, be attributed to desorption of pyridine from Lewis acid centres. Other bases, including cyclohexylamine and butylamine, also desorb at temperatures which have previously been attributed to the desorption of protonated base. Ni2+- and Co2+-exchanged clay contained predominatly Lewis acid or electron accepting sites, which is in marked contrast to the behaviour of trivalent cation exchanged clays.

Heavy-mineral studies on Jurassic sandstones from the central and northern North Sea areas and from the Lossiemouth Borehole (onshore NE Scotland) show that the dissolution of apatite is a function of depositional environment rather than burial depth. In the shallow marine Upper Jurassic sands of the Claymore, Clyde and Tartan Fields, and in the deeper-water Magnus sands, apatite is ubiquitous, even where burial depths exceed 3800 m. Conversely, the fluvio-deltaic sands of the Beatrice, Heather, Ninian and Murchison Fields, and of the Lossiemouth Borehole, have suffered apatite dissolution, although burial depths range from very shallow (Lossiemouth Borehole) to about 3300 m. This clearly indicates that apatite dissolution has taken place through penetration of low-pH meteoric groundwaters at a very early stage in diagenesis, and that high-temperature fluids circulating in deep burial have had little or no effect. This is in accord with patterns of mineral dissolution observed in other sedimentary basins and in the North Sea Palaeocene. Although dissolution of heavy minerals is unlikely to generate significant secondary porosity, the process is nevertheless caused by the same pore-fluids that dissolve major framework constituents. Patterns of heavy-mineral dissolution therefore provide clues to the nature of these pore-fluids. Here, the relative stability of apatite is particularly significant. The order of stability apatite > garnet > kyanite, which characterizes deep burial of North Sea sandstones, has previously been simulated experimentally using fluids of pH 8 at room temperature. This suggests that high-temperature acidic pore-fluids may not have played a significant role in the development of secondary porosity in North Sea sandstones.

Poorly crystallized lepidocrocites precipitated from ferriferous spring waters differ from better crystallized samples by differentially broadened X-ray diffraction lines and higher basal spacings. On the basis of high magnification EM, this was explained as due to the fact that the lath-like crystals consist only of 3–15 unit layers with possibly weakened H-bonding between the layers. These properties are analogous to those of the so called ‘pseudoboehmite’ as compared to boehmite. Poorly crystallized lepidocrocites, exhibiting similar features, were synthesized by oxidation of Fe(II) solutions. From these experiments it was suggested that such lepidocrocite forms in nature by a rapid oxidation of Fe2+ in spring water when it emerges at the surface.

Synthetic 2-line and 6-line ferrihydrites were heated to 400 K, 500 K and 600 K, under dry conditions. Heating to 400 K lowered the ratios of structural OH to Fe2O3 without a phase transformation. The lowest ratios observed at 400 K were 1·23 (2-line) and 0·85 (6-line ferrihydrite) after 1150 h. For 6-line ferrihydrites heated to 400 K, the solubility in oxalate and the BET surface areas decreased with increasing heating time, whereas the unit-cell parameters, the relative peak intensities and the mean coherence lengths did not change significantly. Heating the 2-line ferrihydrites to 400 K produced microporosity.

The crystal-chemical mechanisms by which transition metals are associated with goethite are fundamental to our understanding of the solubility and bioavailability of micronutrients and heavy metals in soils, and in the formation of laterite ore deposits. Transition metals such as Cr, Mn and Ni may sorb onto goethite by forming surface precipitates, surface complexes or by replacing Fe3+ in the goethite structure. In the work reported here, we investigated the local coordination environment of Cr, Mn and Ni in synthetic goethite using EXAFS spectroscopy. We demonstrate the isomorphous substitution for Fe3+ by Cr3+ (up to 8 mol.%), Mn3+ (up to 15 mol.%) and Ni2+ (up to 5 mol.%). We find, however, that the next-nearest-neighbour coordination environment changes with composition. The perturbations are likely to be responsible for limiting the accommodation of Cr3+, Mn3+ or Ni2+ in the FeOOH structure.

The Fourier transform Raman spectra of the kaolinite minerals have been measured in the 50–3800 cm−1 region using near infrared spectroscopy. Kaolinites are characterized by remarkably intense bands in the 120–145 cm−1 region. These bands, attributed to the O-Si-O and O-Al-O symmetric bending modes, are both polymorph and orientation dependent. The 200–1200 cm−1 spectral range is a finger-print region for clay minerals and each kaolinite clay has its own characteristic spectrum. The structure of clays is fundamentally determined by the position of hydroxyl groups. Fourier-transform Raman spectroscopy readily enables the hydroxyl stretching region to be examined allowing identification of the component bands. The advantages of FT-Raman spectroscopy are shown to enhance the study of the kaolinite structure.

The processes taking place during decomposition of montmorillonite by percussive grinding have been studied by IR, X-ray and DTA methods. Destruction can be described as a series of parallel changes in the montmorillonite structure which proceed at various rates. The fastest is a change in status of the exchangeable cations followed by that of the hydroxyl groups. The slowest degradation process is the separation of tetrahedral and octahedral sheets. Degradation of the structure proceeds by delamination of particles, breaking of layers, crushing of layers by shocks perpendicular to the ab-direction, rearrangement of coordination polyhedra and transfer of protons within the structure. The relative importance of each of these processes is evaluated. It is assumed that the matrix resulting from complete breakdown of the montmorillonite structure consists mainly of the residue of tetrahedral sheets and deformed incomplete tetrahedra and octahedra, or of individual atoms held together in clumps either by Van der Waals forces or possibly, in some cases, by newly formed chemical bonds.

A method for the preparation of Ln-montmorillonite (Ln = La, Ce, Sm, Gd, Er and Y) that ensures saturation of the CEC is described and the most favourable equilibrium conditions are discussed. The H+- Ln3+ exchange rate in acid montmorillonite and the effect of concentration and pH on the retention of Ln3+ ions by the clay are also investigated. The presence of montmorillonite modifies the pH value at which precipitation of hydroxides begins, a process that actually occurs at pH ∼ 5.

The pillaring process of montmorillonite and beidellite with Al and Ga polymers has been studied using XRD, IR, 27Al, 71Ga, and 29Si MAS NMR, TGA, TEM, N2 adsorption and chemical analyses. The Al adsorption maximum for montmorillonite is close to 5.5 mEq Al/g clay, whereas the maximum for Ga is higher. Basal spacings of both Ga- and Al-pillared clays vary between 16.7 and 18.8 Å. Freeze-drying of pillared products followed by calcination yielded more regular pillared structures. Pillaring montmorillonite increased the BET surface area from 35 m2/g to 350 m2/g mainly by the creation of micropores <20 Å in diameter. The Al-pillared clays are thermally stable to ∼700°C. Calcination of pillared montmorillonite liberates protons from the pillar, which diffuse into the clay sheet, lowering the thermal stability. In pillared beidellite, mainly silanol groups are formed by breaking Si-O-Al bonds. No reaction is observed between pillars and montmorillonite upon calcination, whereas in pillared beidellite a structural transformation links the pillar to inverted tetrahedra of the tetrahedral sheet. The basal spacing of Ga-pillared montmorillonite collapses to 9.5 Å at 350°C due to the Ga polymer decomposing to Ga3+ cations.

Current thinking regarding the possible origins and probable evolutionary histories of meteorites is summarized. Selected data concerning the composition, petrology and other characteristics of the CI and CM groups of stony meteorites in which layered minerals principally occur are then presented. Layered compounds, mainly phyllosilicates, are shown to form a major part of the fine-grained matrix of the CI and CM meteorites, which are classified as carbonaceous chondrites. The results of recent investigations of matrix mineralogy are reviewed, with particular emphasis on the findings of electron microscopy. Several forms of Fe-Mg-serpentine have been identified as the principal phyllosilicates. ‘Poorly-characterized phases’ in CM meteorites have proved to be tochilinite and intergrowths of tochilinite with serpentines. The results generally indicate that the phyllosilicates and most other matrix minerals formed by aqueous alteration in the regoliths of the CI and CM parent bodies; but there is isotopic evidence for the incorporation of components and possibly mineral grains which predate the solar nebula. It is concluded that more detailed chemical and mineralogical information about the phyllosilicates and associated minerals will enable useful constraints to be placed on the possible identities of their precursors and the environments in which both they and the matrix minerals formed.

The advantages and limits of empirical, semi-empirical and thermodynamic methods devoted to the estimation of chlorite-formation temperature are discussed briefly. The results of semiempirical and thermodynamic approaches with different assumptions regarding the redox state of iron in chlorite are compared for a large set of natural data covering a range of pressure conditions from a few hundred bars to 18 kbar and temperature from 100 to 500°C. The T-XFe3+ evolution estimated using the thermodynamic approach of Vidal et al. (2005) shows a systematic increase in XFe3+ with decreasing temperature, which is compatible with the decrease in aO2 buffered by magnetite- or hematite-chlorite equilibrium. This trend as well as the observed increase in vacancies in chlorite with decreasing temperature is interpreted as the incorporation of Fe3+-sudoite. The standard-state properties of this endmember have been derived to reproduce the observed T-aO2-XFe3+ evolutions. It can be used to estimate T-aO2-XFe3 values with a Chl-Qtz-H2O multi-equilibrium approach. When combining our results with those of other studies published recently, it appears that thermodynamic approaches and mapping techniques developed for metamorphic rocks can be used to discuss the conditions of formation of very low-grade rocks where kinetics is much more sluggish than in metamorphic rocks. This requires use of appropriate analytical tools and techniques with a spatial resolution of a few hundred nanometres.